Electroconductive polymer and process for producing the polymer

ABSTRACT

Electroconductive polymers having a chemical structure represented by, for example, the formula (I) ##STR1## wherein R 1  and R 2  independently represent H, a C 1  to C 20  alkyl or alkoxy group, an amino group, a trihalomethyl group or a phenyl group, X represents S, O, Se, Te or NR 3  R 3  represents H, a C 1  to C 6  alkyl group or an aryl group, M represents a cation such as H + , an alkali metal ion or a quaternary ammonium ion, and m is 0.2 to 2 and a process for producing the polymer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.08/251,297, filed May 31, 1994, and of application Ser. No. 07/985,339,filed Dec. 4, 1992, both are now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention in one embodiment relates to an electroconductivepolymer having a high stability and exhibiting high solubility in waterand also relates to a process for producing the polymer. Morespecifically, the present invention in this embodiment relates to awater-soluble electroconductive polymer particularly suitable for use aselectrodes, sensors, electronic display elements, nonlinear- opticalelements, photoelectric conversion elements, antistatic agents,conducting materials, and optical materials which require highworkability in the field of electric and electronic industry and aprocess for producing the polymer.

The present invention in another embodiment relates to an extremelystable electroconductive polymer having high solvent solubility and to aprocess for producing the polymer. More specifically, the presentinvention relates to the polymer and to a process for producing anelectroconductive polymer particularly suitable as an electrode, asensor, an electronics display element, a non-linear optical element, aphotoelectric conversion element, or an antistatic agent, whichencounters severe processability requirements in the field of electricand electronic industries, as well as being suitable for variouselectroconductive or optical materials.

2. Description of the Related Art

Polymers of an advanced electron conjugate system have attractedattention in industries concerned due to their characteristics such asnot only conductivity but also behavior manifested in the change ofstate during the metal/semiconductor transition. Thus, studies have beenmade with a view to developing these polymers suitable for varyingapplications. Among other polymers of this class, water-solubleself-doping conjugate type polymers which are obtained by having aBronsted acid group joined to the main chain of polymer by covalent bondeither directly or indirectly with the aid of a spacer have arrested aparticular interest in respect that they possess stableelectroconductivity over a long period without needing contribution ofany external dopant.

Specific examples thereof include a polythiophene derivative having analkanesulfonic acid group (F. Wudl et al., Journal of American ChemicalSociety, vol. 109, p. 1858, 1987; and E. E. Havinga et al., PolymerBulletin, vol. 18, p. 277, 1987), a polythiophene derivative or apolypyrrole derivative (Aldissi, U.S. Pat. No. 4,880,508), a polymerhaving an alkanesulfonic acid group or an alkylcarboxyl acid group as asubstituent in an aromatic ring of polyaniline (WO 87/05914;JP-A-63-39916), a polymer having a propanesulfonic acid groupsubstituted at the N-position of pyrrole (J. Chem. Soc., ChemicalCommunication, p. 621, 1987), a polyaniline derivative having apropanesulfonic acid group substituted at the N-position (J. Chem. Soc.,Chemical Communication, p. 180, 1990 and Synthetic Metals, vol. 31, p.369, 1989), a polyaniline derivative having a sulfonic acid groupsubstituted directly on the aromatic ring (J. Am. Chem. Soc., vol. 112,p. 2800, 1990), and a polycarbazole derivative having an alkanesulfonicacid group substituted at the N-position (U.S. Pat. No. 5,130,412). Inaddition, their production processes are also disclosed in thesepublications.

Furthermore, an oxidative chemical polymerization of a thiophenederivative monomer having an alkanesulfonic acid group is disclosed inJP-A-2-189333.

Further, among condensed heteropolycyclic compounds, isothianaphthene,benzo c!furan, and naphtho 2,3-c!thiophene, each having a π-conjugatedquinoid structure, are known to have a very high reactivity, and requirespecific procedures for their isolation (see, J. Org. Chem., vol. 36, p.3932, 1971, and Recl. Tray. Chim. Pays-Bas, vol. 87, p. 1006, 1968).

As a specified example of bicyclic conducting polymers,polyisothianaphthene is disclosed in conjunction with a method for theproduction thereof in J. Org. Chem., 49, 3382 (1984), in which it isdescribed to possess a stable conductivity as evidenced by an extremelysmall energy gap of 1.1 eV. However, polyisothianaphthene is neithersoluble nor fusible and is extremely deficient in moldability. A methodfor rendering this particular polymer soluble in an organic solvent byintroducing an alkyl group or alkoxy group into the polymer is disclosedin JP-A-2-242816. The term "JP-A" as used herein means an "unexaminedpublished Japanese patent application".

The thought that the conductivity of such isothianaphthene polymers isfurther influenced by introducing an electron attracting or donatinggroup into the isothianaphthene backbone has been reported inconjunction with results of calculation by Bredas et al. in J. Chem.Phys., 85(8), 4673 (1986). As examples of the polymers relating to suchisothianaphthene polymers, polymers having a halogen atom as asubstituent as disclosed in JP-A-63-307604 and polymeric compoundspossessing an isothianaphthene backbone having an electron attractinggroup as a substituent as described in JP-A-02-252727 may be cited. Aprocess for producing a polymer having a naphtho 2,3-c!thiophenestructure, which is a heterotricyclic electroconductive polymer that isneither soluble nor fusible, has been reported in Synthetic Metals, vol.35, p. 263, 1990. The oxidative chemical polymerization of1,3-dihydroisothianaphthene without a sulfonic acid group is disclosed,for example, in JP-A-63-118323 and U.S. Pat. No. 4,789,748. Bicyclicwater-soluble conducting polymers, having an isothianaphthenylenestructure, an isobenzofurylene structure, an isoindolylene structure, anisobenzoselenylene structure, or an isobenzotellurylene structure as arepeating unit thereof, have never been disclosed to the art to date.Neither of these patent publications has any specific disclosure of thepolymer having a sulfonic acid group on repeating unit of the presentinvention nor of a method for the production of such a polymer.

SUMMARY OF THE INVENTION

Accordingly, a first object of the present invention is to eliminate theabove-mentioned disadvantages of the prior art and to provide apractical and novel bicyclic water-soluble electroconductive polymerderived from a known compound, a process for producing the polymer andan article processed therefrom.

A further object of the present invention is to provide anelectroconductive polymer and a process for producing anelectroconductive polymer comprising a condensed heteropolycyclicmonomer unit having a sulfonic acid group by polymerizing a sulfonicacid group-containing condensed heteropolycyclic compound as a startingmaterial.

Another object of the present invention is to provide a process forproducing an electroconductive polymer comprising a condensedheteropolycyclic monomer unit having a sulfonic acid group bypolymerizing a sulfonic acid group-containing condensed heteropolycycliccompound as a starting material alone or together with another aromaticcompound and/or heterocyclic compound and/or compound capable of forminga π-electron conjugated structure.

Other objects and advantages of the present invention will be apparentfrom the following description.

In accordance with a first embodiment of the present invention, there isprovided a water-soluble electroconductive polymer having a chemicalstructure represented by the formula (I): ##STR2## wherein R¹ and R²independently represent a hydrogen atom, a linear or branched alkyl oralkoxy group having 1 to 20 carbon atoms, a primary, secondary ortertiary amino group, a trihalomethyl group, a phenyl group or asubstituted phenyl group, X represents S, O, Se, Te or NR³, R³represents a hydrogen atom, a linear or branched alkyl group having 1 to6 carbon atoms or a substituted or unsubstituted aryl group, providingthat the chain in the alkyl group of R¹, R² or R³ or in the alkoxy groupof R¹ or R² optionally contains a carbonyl, ether or amide bond, Mrepresents H⁺, an alkali metal ion such as Na⁺, Li⁺ or K⁺ or a cationsuch as a quaternary ammonium ion, and m represents a numerical value inthe range between 0.2 and 2.

In accordance with a second embodiment of the present invention, thereis also provided a water-soluble electroconductive polymer having achemical structure represented by the formula (II): ##STR3## wherein R¹,R², X, R³, M, and m have the same meanings as defined above with respectto the formula (I) and k is a numerical value smaller than that of m,and/or the formula (III): ##STR4## wherein R¹, R², X, R³, M, and m havethe same meanings as defined above with respect to the formula (I), δ isa numerical value not more than 0.7, Z represents an anion, and jrepresents a numerical value 1 or 2 indicating the valency of the anionZ, as obtained by electrochemically and/or chemically doping theabove-mentioned polymer having a chemical structure represented by theformula (I).

In accordance with a third embodiment of the present invention, there isprovided a process for producing the water-soluble electroconductivepolymer mentioned above, which process comprises reacting a sulfonatingagent with a compound having the formula (IV): ##STR5## wherein R¹, R²,and R³ have the same meanings as defined above with respect to theformula (I) and Y represents S, O, Se, Te, S═O, Se═O, Te═O or NR³ andthe general formula (V): ##STR6## wherein R¹, R², X and R³ have the samemeanings as defined above with respect to the formula (I) or on at leastone compound selected from the compounds mentioned above.

The present invention in a fourth embodiment provides anelectroconductive polymer comprising at least one structural unitrepresented by formula (VII) as a repeating unit and a process forproducing such, which comprises polymerizing a compound represented byformula (VI): ##STR7## wherein R⁴, R⁵, R⁶, R⁷ and R⁸ each independentlyrepresents a monovalent group selected from the group consisting of ahydrogen atom, a linear or branched, saturated or unsaturated alkyl,alkoxy, or alkyl ester group each having from 1 to 20 carbon atoms,preferably from 1 to 12 carbon atoms, SO₃ ⁻ M¹, a halogen atom, a nitrogroup, a cyano group, a primary, secondary or tertiary amino group, atrihalomethyl group, and a substituted or unsubstituted phenyl group,with the proviso that two or more of R⁴, R⁵, R⁶, R⁷ and R⁸ are not SO₃ ⁻M¹ simultaneously, wherein the hydrocarbon chain represented by R⁴, R⁵,R⁶, R⁷ or R⁸ may combine with each other at any optional position toform at least one divalent chain which forms, together with two carbonatoms of the substituted ring, at least one 3- to 7-membered saturatedor unsaturated hydrocarbon ring structure, and the alkyl group, thealkoxy group, or the alkyl ester group represented by R⁴, R⁵, R⁶, R⁷ andR⁸, or the cyclic hydrocarbon chain formed therefrom may optionally havea bond giving rise to a carbonyl, ether, ester, amide, sulfide,sulfinyl, sulfonyl or imino moiety; wherein X¹, X², X³ and X⁴ eachindependently represents a hydrogen atom or a halogen atom; wherein M¹represents H⁺, an alkali metal ion, such as Na⁺, Li⁺ and K⁺, or a cationof a Vb Group element unsubstituted or substituted with an alkyl grouphaving from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms,and more preferably from 1 to 12 carbon atoms, or with an aryl grouphaving from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms,more preferably from 6 to 16 carbon atoms, such as NH₄ ⁺, NH(CH₃)₃ ⁺,N(CH₃)₄ ⁺, NH(C₂ H₅)₃ ⁺, N(C₆ H₅)₄ ⁺, PH₄ ⁺, P(CH₃)₄ ⁺, P(C₆ H₅)₄ ⁺,AsH₄ ⁺, As(CH₃)₄ ⁺ and As(C₆ H₅)₄ ⁺ ; and wherein r represents aninteger of from 0 to 3, and indicates the number of condensed ringsenclosed by the dihydrothiophene ring and the benzene ring havingsubstituents R⁴, R⁵ and R⁶, wherein the condensed ring in the formulamay optionally contain nitrogen or an N-oxide: ##STR8## wherein R⁴, R⁵,R⁶, R⁷, R⁸, M¹ and r each has the same meaning as defined above.

The present invention in a fifth embodiment also provides a process forproducing an electroconductive polymer comprising a chemical structurerepresented by formula (VIII): ##STR9## wherein R⁴, R⁵, R⁶, R⁷, R⁸, M¹and r each has the same meaning as described above, Ar represents arepeating unit of a π-electron conjugated system having no sulfonic acidgroup, p and q represent molar fractions of the respective repeatingunits in the copolymer, and thus do not denote a block copolymer and aprocess for producing such by polymerizing a compound represented byformula (VI), wherein R⁴, R⁵, R⁶, R⁷, R⁸, X¹, X², X³, X⁴, M¹ and r eachhas the same meaning as described above, alone or together with anotheraromatic compound and/or heterocyclic compound and/or compound capableof forming a π-electron conjugated structure.

The present invention further provides in a sixth embodiment anelectroconductive polymer comprising a chemical structure represented byformula (IX): ##STR10## wherein R⁴, R⁵, R⁶, M¹, Ar, p and q each has thesame meaning as described above, by polymerizing a compound representedby formula (VI), wherein R⁴, R⁵, R⁶, R⁷, R⁸, X¹, X², X³, X⁴ and M¹ eachhas the same meaning as described above and r is 0, alone or togetherwith another aromatic compound and/or heterocyclic compound and/orcompound capable of forming a π-electron conjugated structure.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be better understood from the description setforth below with reference to the accompanying drawings, wherein:

FIG. 1 is a UV spectrum of the polymer obtained in Example 1;

FIG. 2 is a gel permeation chromatograph of the polymer obtained inExample 1;

FIG. 3 is an infrared absorption spectrum of the polymer obtained inExample 1;

FIG. 4 shows a cyclic voltammogram performed on the film of the polymerobtained in Example 1;

FIG. 5 is a UV spectrum of the polymer obtained in Example 2;

FIG. 6 is the visible near infrared absorption spectrum of the polymerobtained in Example 21;

FIG. 7 is the visible near infrared absorption spectrum of the polymerobtained in Example 22; and

FIG. 8 is the visible near infrared absorption spectrum of the polymerobtained in Example 24.

DETAILED DESCRIPTION OF THE INVENTION

The substituents R¹ and R² of the polymer having a chemical structurerepresented by the formula (I) according to the present invention areonly required to be those inhibiting neither the reaction of sulfonationnor the polymerization reaction of monomers. For example, they areindependently selected from those among a hydrogen atom, linear orbranched alkyl or alkoxy groups having 1 to 20 carbon atoms, aliphaticor aromatic primary, secondary or tertiary amino groups, trihalomethylgroups such as trichloromethyl, phenyl group, and substituted phenylgroups. Optionally, the above-mentioned alkyl or alkoxy groups maycontain a carbonyl, ether, or amide bond in their chains having 1 to 20carbon atoms.

Specific examples of R¹ and R² are hydrogen, alkyl groups and alkoxygroups. More specific examples of such alkyl groups include methyl,ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, dodecyl,methoxyethyl, ethoxyethyl, acetonyl, phenacryl and the like, and thoseof such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy,octyloxy, dodecyloxy and the like.

Other specific examples of R¹ and R² include amino groups such asmethylamino, ethylamino, diphenylamino, anilino, and the like,trifluoromethyl group, phenyl group, tolyl group, xylyl group, acylamidogroups such as acetoamido and the like.

The symbol m which means the ratio of substitution of "sulfo"-containinggroup at the benzene ring of the polymer represents a numerical value inthe range between 0.2 and 2, and the range between 0.4 and 1.3 ispreferably represented.

The symbol X in the formula (I) represents S, O, Se, Te or NR³ and thusthe chemical structure represented by formula (I) is aisothianaphthenylene, isobenzofurylene, isobenzoselenylene,isobenzotellurylene, or isoindolylene structure. The substituent R³mentioned above represents a linear or branched alkyl group having 1 to6 carbon atoms or substituted or unsubstituted aryl group. The alkylgroups in the substituents R³ may optionally contain a carbonyl, ether,or amide bond in its chain having 1 to 6 carbon atoms.

Specific examples of R³ are hydrogen, methyl, ethyl, propyl, isopropyl,butyl, hexyl, phenyl, tolyl, methoxyethyl, ethyoxyethyl, acetonyl,acetyl and the like.

The symbol M represents H⁺, an alkali metal ion such as Na⁺, Li⁺ or K⁺,or a cation such as ammonium or an alkyl-substituted or aryl-substitutedcation of Vb group element such as N(CH₃)₄ ⁺ or N(C₆ H₅)₄ ⁺. Theconversion to the specific cation is easily effected by means of anordinary ion-exchange resin.

The condensed heteropolycyclic compound represented by formula (VI) is acompound wherein r of formula (VI), which indicates the number of thecondensed rings enclosed by the dihydrothiophene ring and the benzenering having substituents R⁴, R⁵ and R⁶, is an integer of from 0 to 3,and the condensed rings of formula (VI) may optionally contain nitrogenor an N-oxide. Suitable examples include thieno 3,4-b!quinoxaline andthieno 3,4-b!quinoxaline-4,9-dioxide. The hydrocarbon chain representedby R⁴, R⁵, R⁶, R⁷ or R⁸ may combine with each other at any optionalposition to form at least one divalent chain which forms, together withtwo carbon atoms of the substituted ring, at least one 3- to 7-memberedsaturated or unsaturated hydrocarbon ring structure. The alkyl group,the alkoxy group, or the alkyl ester group represented by R⁴, R⁵, R⁶, R⁷and R⁸, or the cyclic hydrocarbon chain formed therefrom may optionallyhave a bond giving rise to a carbonyl, ether, ester, amide, sulfide,sulfinyl, sulfonyl or imino.

Specific examples of the basic skeleton for the condensedheteropolycyclic compound represented by formula (VI) include1,3-dihydroisothianaphthene (a compound where in formula (VI), r is 0,and X¹, X², X³ and X⁴ each is H), 1,3-dichloroisothianaphthene (acompound where in formula (VI), r is 0, X¹ and X³ each is Cl, and X² andX⁴ each is H), 1,1,3,3-tetrachloroisothianaphthene (a compound where informula (VI), r in 0 and X¹, X², X³ and X⁴ each is Cl),1,3-dihydronaphtho 1,2-c!thiophene (a compound where in formula (VI), rin 1, and X¹, X², X³ and X⁴ each is H), 1,3-dihydronaphtho2,3-c!thiophene (a compound where in formula (VI), r is 1 and X¹, X², X³and X⁴ each is H), 1,3-dichloronaphtho 2,3-c!thiophene (a compound wherein formula (VI), r is 1 and X¹ and X³ each is Cl, and X² and X⁴ each isH), 1,3-dihydroanthra 1,2-c!thiophene (a compound where in formula (VI),r is 2, and X¹, X², X³ and X⁴ each is H), 1,3-dihydroanthra2,3-c!thiophene (a compound where in-formula (VI), r is 2, and X¹, X²,X³ and X⁴ each is H), 1,3-dihydrophenanthra 1,2-c!thiophene (a compoundwhere in formula (VI), r is 2, and X¹, X², X³ and X⁴ each is H),1,3-dihydrophenanthra 2,3-c!thiophene (a compound where in formula (VI),r is 2, and X¹, X², X³ and X⁴ each is H), 1,3-dihydrophenanthra3,4-c!thiophene (a compound where in formula (VI), r is 2 and X¹, X², X³and X⁴ each is H), 1,3-dihydrophenanthra 9,10-c!thiophene (a compoundwhere in formula (VI), r is 2 and X¹, X², X³ and X⁴ each is H),1,3-dihydronaphthaceno 1,2-c!thiophene (a compound where in formula(VI), r is 3 and X¹, X², X³ and X⁴ each is H), and1,3-dihydronaphthaceno 2,3-c!thiophene (a compound where in formula(VI), r is 3 and X¹, X², X³ and X⁴ each is H), but the present inventionshould not be construed as being limited thereto.

Examples of the 3- to 7-membered saturated or unsaturated hydrocarboncyclic structures formed by combining the hydrocarbon chain representedby R⁴, R⁵, R⁶, R⁷ or R⁸ with each other at an optional position include1,3-dihydroperylo c!thiophene and 1,3-dihydroacenaphtho c!thiophenestructures, but the present invention should not be construed as beinglimited thereto.

Further, of the compounds represented by formula (VI), examples of thecondensed heterocyclic compounds containing nitrogen in the condensedring include the following compounds, but the present invention shouldnot be construed as being limited thereto. ##STR11##

Preferred examples of the basic skeleton in the present inventioninclude a compound having a 1,3-dihydroisothianaphthene structurerepresented by formula (X): ##STR12## wherein R⁴, R⁵ and R⁶ eachindependently represents a monovalent group selected from the groupconsisting of a hydrogen atom, a linear or branched, saturated orunsaturated alkyl, alkoxy or alkyl ester group each having from 1 to 20carbon atoms, preferably from 1 to 12 carbon atoms, SO₃ ⁻ M¹, a halogenatom, a nitro group, a cyano group, a primary, secondary, or tertiaryamino group, a trihalomethyl group, and a substituted or unsubstitutedphenyl group, with the proviso that two or more of R⁴, R⁵ and R⁶ are notSO₃ ⁻ M¹ simultaneously, the hydrocarbon chain represented by R⁴, R⁵ orR⁶ may combine with each other at any optional position to form at leastone divalent chain which forms, together with two carbon atoms of thesubstituted ring, at least one 3- to 7-membered saturated or unsaturatedhydrocarbon ring structure, and the alkyl group, the alkoxy group, orthe alkyl ester group represented by R⁴, R⁵ and R⁶, or the cyclichydrocarbon chain formed therefrom may optionally have a bond givingrise to a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl orimino; X¹, X², X³ and X⁴ each independently represents a hydrogen atomor a halogen atom; M¹ represents H⁺, an alkali metal ion, such as Na⁺,Li⁺ and K⁺, or a cation of a Vb Group element unsubstituted orsubstituted with an alkyl group having from 1 to 30 carbons atoms,preferably from 1 to 20 carbon atoms, more preferably from 1 to 12carbon atoms, or with an aryl group having from 6 to 30 carbon atoms,preferably from 6 to 20 carbon atoms, more preferably from 6 to 16carbon atoms, such as NH₄ ⁺, NH(CH₃)₃ ⁺, N(CH₃)₄ ⁺, NH(C₂ H₅)₃ ⁺, N(C₆H₅)₄ ⁺, PH₄ ⁺, P(CH₃)₄ ⁺, P(C₆ H₅)₄ ⁺, ASH₄ ⁺, As(CH₃)₄ ⁺ and As(C₆ H₅)₄⁺, and a compound having a 1,3-dihydronaphtho 2,3-c!thiophene structurerepresented by formula (XI): ##STR13## wherein R⁴, R⁵, R⁶, R⁷, R⁸, X¹,X², X³, X⁴ and M¹ each has the same meaning as in formula (VI).

Useful examples of the substituents R⁴, R⁵, R⁶, R⁷ and R⁸ in formulae(VI), (VII), (VIII) and (XI), and the substituents R⁴, R⁵ and R⁶ informulae (IX) and (X) include a hydrogen atom, a halogen atom, SO₃ ⁻ M¹,a saturated alkyl group, an unsaturated alkyl group, a saturated alkoxygroup, an unsaturated alkoxy group, a saturated alkyl ester group, anunsaturated alkyl ester group, a nitro group, and a cyano group. Morespecific examples of the substituents include chlorine, bromine,fluorine and iodine as a halogen atom, methyl, ethyl, propyl, isopropyl,butyl, t-butyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, methoxyethyl,ethoxyethyl, (2-methoxy)ethyl, acetonyl, vinyl, 1-methylethenyl,2-methylethenyl, 2-methylethenyl, crotonyl, allyl, phenyl, tolyl, xylyl,and phenacyl as the hydrocarbon chain of the saturated or unsaturatedalkyl or alkyl ester group, and methoxy, ethoxy, (2-methoxy)ethoxy,propoxy, isopropoxy, hexyloxy, octyloxy, and dodecyloxy as the alkoxygroup.

In addition to the foregoing, examples of the substituents include anamino group, such as methylamino, ethylamino, diphenylamino, andanilino, and a group, such as trifluoromethyl, chlorophenyl, andacetamide.

Useful examples of the substituents X¹, X², X³ and X⁴ in formulae (VI),(X) and (XI) include hydrogen, fluorine, chlorine, bromine, and iodine.

More specific examples of the compounds represented by formula (X)include 1,3-dihydroisothianaphthene-5sulfonic acid,1,3-dichloroisothianaphthene-5-sulfonic acid,1,3-dibromoisothianaphthene-5-sulfonic acid,1,1,3,3-tetrachloroisothianaphthene-5-sulfonic acid,1,3-dihydro-6-methoxyisothianaphthene-5-sulfonic acid,1,3-dichloro-6-methoxyisothianaphthene-5-sulfonic acid,1,3-dihydro-6-butoxyisothianaphthene-5-sulfonic acid,1,3-dihydro-6-decyloxyisothianaphthene-5-sulfonic acid,1,3-dihydro-6-methoxycarbonylisothianaphthene-5-sulfonic acid,1,3-dihydro-4,7-dimethoxyisothianaphthene-5-sulfonic acid,1,3-dihydroisothianaphthene-5,6-disulfonic acid,1,3-dibromo-4,7-dimethoxyisothianaphthene-5-sulfonic acid,1,3-dihydro-5,6-dioxymethyleneisothianaphthene-4-sulfonic acid,1,3-dihydro-6-nitroisothianaphthene-5-sulfonic acid,1,3-dihydro-6-bromoisothianaphthene-5-sulfonic acid,1,3-dihydro-6-cyanoisothianaphthene-5-sulfonic acid,1,3-dihydro-6-aminoisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-trifluoromethylisothianaphthene-5-sulfonic acid, and a lithium salt,a sodium salt, a potassium salt, an ammonium salt, and a quaternaryammonium salt of these sulfonic acid derivatives, but the presentinvention should not be construed as being limited thereto.

More specific examples of the compounds represented by formula (XI)include 1,3-dihydronaphtho 2,3-c!thiophene-5-sulfonic acid,1,3-dichloronaphtho 2,3-c!thiophene-5-sulfonic acid, 1,3-dibromonaphtho2,3-c!thiophene-5-sulfonic acid, 1,3-dihydronaphtho2,3-c!thiophene-6-sulfonic acid, 1,1,3,3-tetrachloronaphtho2,3-c!thiophene-5-sulfonic acid, 1,3-dihydro-7-methoxynaphtho2,3-c!thiophene-6-sulfonic acid, 1,3-dihydro-5,7-dimethoxynaphtho2,3-c!thiophene-6-sulfonic acid, 1,3-dibromo-5,7-dimethoxynaphtho2,3-c!thiophene-6-sulfonic acid, 1,3-dihydro-6,7-dioxymethylenenaphtho2,3-c!thiophene 5-sulfonic acid, 1,3-dihydro-8-methoxycarbonylnaphtho2,3-c!thiophene-6-sulfonic acid, 1,3-dihydro-7-nitronaphtho2,3-c!thiophene-5-sulfonic acid, 7-bromo-l,3-dihydronaphtho2,3-c!thiophene-5-sulfonic acid, 7-cyano-1,3-dihydronaphtho2,3-c!thiophene-5-sulfonic acid, 1,3-dihydro-7-methylnaphtho2,3-c!thiophene-6-sulfonic acid, 1,3-dihydro-6,7-dimethylnaphtho2,3-c!thiophene-5-sulfonic acid, 1,3-dihydro-7-trifluoromethylnaphtho2,3-c!thiophene-5-sulfonic acid, and a lithium salt, a sodium salt, apotassium salt, an ammonium salt, and a quaternary ammonium salt ofthese sulfonic acid derivatives, but the present invention should not beconstrued as being limited thereto.

In the compound represented by formula (VI), (X) or (XI), theelectroconductive polymer comprising at least one structural unitrepresented by formula (VII), and the electroconductive polymercomprising a structure represented by formula (VIII) or (IX), thecounter cation of the sulfonic acid ion is H⁺, an alkali metal ion, suchas Na⁺, Li⁺ and K⁺, or a cation of a Vb Group element unsubstituted orsubstituted with an alkyl group having from 1 to 30 carbon atoms,preferably from 1 to 20 carbon atoms, more preferably from 1 to 12carbon atoms, or with an aryl group having from 6 to 30 carbon atoms,preferably from 6 to 20 carbon atoms, more preferably from 6 to 16carbon atoms, such as NH₄ ⁺, NH(CH₃)₃ ⁺, N(CH₃)₄ ⁺, NH(C₂ H₅)₃ ⁺, N(C₆H₅)₄ ⁺, PH₄ ⁺, P(CH₃)₄ ⁺, P(C₆ H₅)₄ ⁺, AsH₄ ⁺, As(CH₃)₄ ⁺ and As(C₆ H₅)₄⁺. In these formulae, M¹ may be a plurality of different cationsselected from the above-described cations. The conversion into aspecific cation may be conducted by ion exchange into a desired cationby using a conventional ion-exchange resin or a dialysis membrane.

X¹, X², X³ and X⁴ in formulae (VI), (X) and (XI) each independentlyrepresents a hydrogen atom or a halogen atom. The halogen is preferablychlorine, bromine or iodine, and more preferably chlorine or bromine.

When the cation represented by M¹ is H⁺, the electroconductive polymerhaving a main chain of a π-electron conjugated structure and comprisinga chemical structure represented by formula (.VII), (VIII) or (IX)exhibits a self-doping state in an aqueous solution without the help ofan external dopant, and in particular, may exhibit a gel state at a highconcentration. Further, by changing the cation represented by M¹, thesolubility in various solvents, or the affinity to the solvent, can bevaried.

The electroconductive copolymer comprising a chemical structurerepresented by formula (VIII) according to this embodiment of thepresent invention is a copolymer comprising at least one structural unitrepresented by formula (VII) as a repeating unit and another repeatingunit of a π-electron conjugated structure in the main chain structure ofthe polymer. Examples of the repeating unit of the π-electron conjugatedstructure include vinylene, an aromatic structure and a heterocyclicstructure. Examples of the aromatic structure and the heterocyclicstructure include isothianaphthenylene, isobenzofurylene,isobenzoindolylene, isobenzoselenylene, isobenzotellurylene, thienylene,pyrrolylene, furylene, selenylene, tellurylene, iminophenylene andphenylene structures. A plurality of these skeleton structures may bepresent. Further, the repeating unit of the above-described π-electronconjugated structure may be substituted with a substituent which doesnot inhibit the polymerization. Suitable substituents include any ofthose described above for R⁴, R⁵, R⁶, R⁷ and R⁸.

In the electroconductive copolymer comprising a chemical structurerepresented by formula (VIII), p and q represent the molar fractions ofthe respective repeating units in the copolymer as described above.Accordingly, p and q of formula (VIII) do not denote a block copolymer.With respect to the molar fractions of the above-described copolymer(p:q, with the proviso that p+q=1), p as the molar fraction of therepeating unit composed of the structural unit represented by formula(VII) is preferably from 0.05 to 0.95, more preferably from 0.2 to 0.9and most preferably from 0.4 to 0.9. The larger the p value, the greaterthe water solubility.

The molecular weight of the water-soluble electroconductive polymer ofthe present invention of the formula (I), (II) and (III), is in therange between 1,000 and 500,000, preferably between 10,000 and 100,000.

Moreover, the polymer comprising at least one structural unitrepresented by formula (VII) as a repeating unit and the copolymercomprising a chemical structure represented by formula (VIII) or (IX)have a molecular weight of from 1,000 to 500,000, preferably from 10,000to 100,000.

A process for producing an electroconductive polymer comprising achemical structure represented by formula (VII) or an electroconductivecopolymer comprising a chemical structure represented by formula (VIII)or (IX) comprises the homopolymerization or copolymerization of thecompound having a chemical structure represented by formula (VI), (X) or(XI), or the above-described compound and another aromatic compound,and/or heterocyclic compound, and/or compound capable of formingπ-electron conjugated structure.

The compound having a chemical structure represented by formula (VI),(X) or (XI) can be polymerized alone or in the presence of anotheraromatic and/or heterocyclic compounds of a π-electron conjugatedstructure and/or a compound capable of forming a π-electron conjugatedstructure, under an elevated temperature or at room temperature or at alow temperature or while raising the temperature, favored by the actionof the oxidizing agent employed. Accordingly, the polymer comprising achemical structure represented by formula (VII) or the copolymercomprising a chemical structure represented by formula (VIII) or (IX)can be produced very efficiently.

In particular, when the compound having a chemical structure representedby formula (VI), (X) or (XI) is subjected to the polymerization reactionat a high temperature where a sulfonic acid group is readily released, acopolymer comprising a chemical structure represented by formula (VIII)or (IX) is obtained.

Examples of the oxidizing agent which brings about an oxidativedehydrogenation reaction in the polymerization generally include asulfonating reagent, such as sulfuric acid, fuming sulfuric acid, sulfurtrioxide, chlorosulfuric acid, fluorosulfuric acid and amidosulfuricacid, and an oxygen-oxidizing agent using ozone, a peroxide, a peracid,a quinone, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone,tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzo quinone, andtetracyano-1,4-benzoquinone, halogen, such as iodine and bromine,anhydrous aluminum chloride/copper(I) chloride, anhydrous iron(III)chloride, a vanadium-, manganese- or nickel-based metal complex, and acombination of these oxidizing agents. However, there is no particularrestriction on the oxidizing agent.

The addition amount of the oxidizing agent varies depending upon thecompound having a chemical structure represented by formula (VI), (X) or(XI), and the kind of the oxidizing agent used, and cannot be absolutelydetermined. However, in general, the oxidizing agent is preferably usedin an amount of from 1.1- to 20-fold equivalent, more preferably from 2-to 5-fold equivalent, of the compound.

The concentration of the compound having a chemical structurerepresented by formula (VI), (X) or (XI) used in the process of thepresent invention varies depending upon the kind of the compound, thereaction scale, and the kind of chemical compound, such as solventand/or the absence or presence thereof. However, in general, theconcentration of the compound is preferably from 10⁻³ to 10 mol/liter,more preferably from 10⁻² to 1 mol/liter.

The reaction temperature is determined according to the reaction methodemployed, and cannot be specifically restricted. However, in general,the reaction temperature is preferably from -70° C. to 250° C., morepreferably from 0° C. to 150° C. Further, although the chemicalstructure never imposes any restriction on the reaction temperature, itis preferably 70° C. or higher when a copolymer comprising a chemicalstructure represented by formula (VIII) or (IX) is produced using only acompound having a chemical structure represented by formula (VI), (X) or(XI).

The reaction time varies depending upon the reaction method, thereaction temperature, the reaction pressure, or the chemical structureof the compound and cannot be absolutely defined. However, in general,it is preferably from 0.01 hour to 240 hours, more preferably from 0.1hour to 24 hours. The reaction pressure is preferably a normal pressure,but may be from 10⁻⁵ to 100 atm, and more preferably from 1 to 10 atm.

The substitution ratio of the sulfonic acid group of the repeating unitsin the polymer can be decreased by raising the temperature during thereaction up to 60 to 150° C., for 10 min to 20 hours, preferably up to80° to 120° C., for 30 min to 10 hours.

The reaction solvent, which is used if desired, varies depending uponthe reaction temperature, the reaction time, the oxidizing agent and thechemical structure of the compound used, and cannot be absolutelydetermined. However, any solvent may be used as long as the solventdissolves the compound or the oxidizing agent, and does not inhibit thepolymerization reaction. Specific examples of the solvent include water,sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionicacid, acetic anhydride, an ether, such as tetrahydrofuran, dioxane anddiethyl ether, a polar solvent, such as dimethylformamide, acetonitrile,benzonitrile, N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO), anester, such as ethyl acetate and butyl acetate, and a non-aromaticchlorine-based solvent, such as chloroform and methylene chloride. Amixed solvent of these solvents may also be used.

The thus produced polymer comprising at least one structural unitrepresented by formula (VII) as a repeating unit or copolymer comprisinga chemical structure represented by formula (VIII) or (IX) exhibits highsolubility in the solvent, and also has a water solubility due to thesulfonic acid group. Because of these characteristics, the polymer orcopolymer can be isolated and purified through ultrafiltration, dialysisand/or ion-exchange operations. In the case when the polymer comprisinga chemical structure represented by formula (VII) or the copolymercomprising the chemical structure represented by formula (VIII) or (IX)is obtained as a precipitant from the reaction solvent, the polymer orthe copolymer can be isolated and purified through filtration,reprecipitation and/or solvent fractionation.

The copolymer comprising the chemical structure represented by formula(VIII) or (IX) is produced by polymerizing the compound represented byformula (VI), (X) or (XI) in the presence or with the sequentialaddition of another aromatic and/or heterocyclic compound of aπ-electron conjugated structure, and/or a compound capable of forming aπ-conjugated structure after the reaction.

Examples of the aromatic compound and the heterocyclic compound usedherein include isothianaphthene, isobenzofuran, isobenzoindoline,isobenzoselenaphene, isobenzoterenaphene, thiophene, pyrrole, furan,selenophene, tellurophene, aniline, benzene, naphtho 2,3-c!thiophene,anthra 2,3-c!thiophene, naphthaceno 2,3-c!thiophene, pentaceno2,3-c!thiophene, perylo 2,3-c!thiophene, acenaphtho 2,3-c!thiophene andtheir derivatives having various substituents. Suitable substituentsinclude any of those described above for R⁴, R⁵, R⁶, R⁷ and R⁸.

Examples of the compound capable of forming a conjugated structure afterthe reaction include a 1,3-dihydro form, a 1,3-dihalogeno form, a1,1,3,3-tetrahalogeno form and a 2-oxide form of the above-describedisothianaphthene, 5-alkoxyisothianaphthene,5,6-dialkoxyisothianaphthene, naphtho 2,3-c!thiophene, anthra2,3-c!thiophene, naphthaceno 2,3-c!thiophene, pentaceno 2,3-c!thiophene,perylo 2,3-c!thiophene, and acenaphtho 2,3-c!thiophene.

A compound containing nitrogen in the condensed ring may also be used,and examples thereof include 1,3-dihydrothieno c!pyridine,1,3-dihydrothieno c!pyrazine, 1,3-dihydrothieno c!pyridazine and1,3-dihydrothieno c!quinoxaline. Of these, preferred are compounds whichform a thiophene, isothianaphthene, pyrrole, aniline or naphthoc!thiophene structure.

In the process for producing the copolymer according to the presentinvention, the content of the sulfonic acid group in the polymercomprising a chemical structure represented by formula (VIII) or (IX)can be easily controlled by changing the charging ratio of the compoundrepresented by formula (VI), (X) or (XI), and the aromatic compound, theheterocyclic compound or the compound capable of forming a conjugatedstructure. Further, the properties of the polymer comprising a chemicalstructure represented by formula (VIII) or (IX) can be easily controlledby changing the kind or ratio of the aromatic compound, the heterocycliccompound or the compound capable of forming a conjugated structure to becopolymerized therewith.

The water- and/or organic solvent-soluble electroconductive polymerobtained by polymerizing the compound having the chemical structurerepresented by formula (VI), (X) or (X I) according to the presentinvention shows a small energy gap as a semiconductor, and a highconductivity at a low doping level as compared with knownelectroconductive polymers, for example, a polythiophene derivative(disclosed in JP-A-2-242816), and has been found to be very stable inits electroconductive state. Further, due to the effect of the sulfonicacid group as a substituent, a self-doping state readily arises.

In the present invention, an electroconductive polymer comprising achemical structure represented by formula (VII) or (VIII) can be veryefficiently produced by reacting an oxidizing agent with the condensedheteropolycyclic compound having a sulfonic acid group represented byformula (VI). The condensed heteropolycyclic compound of a π-electronconjugated system, such as isothianaphthene and naphtho c!thiophene, isvery highly reactive and hard to deal with during production. However,the sulfonic acid group-containing 1,3-dihydroheteropolycyclic compoundrepresented by formula (VI) is very stable and can-be easily handled inrespective unit operations for producing the compound. In other words,the present invention makes it feasible to produce a sulfonic acidgroup-containing electroconductive polymer or copolymer by thepolymerization of a sulfonic acid group-substituted condensedheteropolycyclic compound having a 1,3-dihydro structure as a monomer.

Among those polymers having a chemical structure represented by any ofthe formula (I), (II) and (III), a polyisothianaphthene derivative(i.e., S for X in the formula (I), (II) or (III) has such a small energygap as about 1.0 eV as a semiconductor, which is smaller than that of aknown water-soluble electroconductive polymer such as a polythiophenederivative having a sulfoalkyl group as a substituent, and ischaracterized by exhibiting high conductivity at a low doping level andhaving high stability in its conductivity. Therefore, the presentpolymer has sufficiently weak absorbance in the visible ray region,particularly in a doped state, so that it can serve as a transparentconducting material having high stability in its conductivity.

The process for producing a polymer according to the present inventionprovides a practical and novel bicyclic water-soluble electroconductivepolymer by reacting a sulfonating agent with a compound represented bythe formula (IV) or formula (V). This process using the sulfonatingagent provides the novel bicyclic water-soluble electroconductivepolymer from a relevant monomer by simultaneously effecting thepolymerization reaction and the sulfonating reaction in one step. Thus,it constitutes itself a novel method of production. Namely, the processof the present invention for producing compounds represented by theformulas (I), (II) and (III) is a particularly effective means forproducing the bicyclic water-soluble electroconductive polymer from saidmonomer compound by said reactions effected in one step. This advantageis well appreciated because such a bicyclic electroconductive polymer aspolyisothianaphthene is infusible and insoluble in organic solvents orin Bronsted acid such as mineral acids and accordingly, the sulfonationdoes not proceed like polyaniline which is soluble in organic solvents.

The water-soluble electroconductive polymer having a chemical structurerepresented by the formula (I) produces an amphoteric water-solubleelectroconductive polymer having a chemical structure represented by theformula (II) and/or (III) by electrochemical or chemical oxidation.

Conversely, the polymer having a chemical structure represented by theformula (II) and/or (III) converts itself into a polymer having achemical structure represented by the formula (I) by electrochemical orchemical reduction. Thus, the polymer having a chemical structurerepresented by the formula (I) and the polymer having a chemicalstructure represented by the formula (II) and/or (III) can be reversiblydoped and de-doped by an oxidation/reduction reaction.

The doping mentioned above can be effected by any of the knownelectrochemical and chemical methods. For example, electrochemicaldoping method which comprises nipping a water-soluble electroconductivepolymer film between opposed electrodes, placing the nipped film in asolution containing a dopant, and applying a potential to the electrodesmay be adopted. For chemical doping, the gaseous phase method whichcomprises causing a dopant such as iodine in the gaseous phase to reacton a water-soluble electroconductive polymer film may be used (See"Fundamental Principles and Applications of ConductingPolymers--Synthesis, Physical Properties, Evaluation, and AppliedTechnologies", page 245-259, I.P.C.).

The dopants which are effectively usable in the reaction underdiscussion (represented by the symbol Z in the formula (III)) includehalogenide anions of Vb group elements such as PF₆ ⁻, AsF₆ ⁻ and SbF⁶⁻,halogenide anions of IIIb group elements such as BF₄ ⁻, halogen anionssuch as I⁻ (I₃ ⁻), Br⁻ and Cl⁻, perhalogenate anions such as ClO₄ ⁻,Lewis acid, protonic acid, electrolytic anions and polyelectrolyticanions, for example. The dopant does not need to be limited to theseexamples. Optionally, two or more such dopants may be used incombination.

Now, the process to be employed in producing the water-solubleelectroconductive polymer of the present invention of the formula (I),(II) and/or (III) will be described below.

The polymer having a chemical structure represented by the formula (I),(II) and/or (III) can be produced by reacting a sulfonating agent suchas fuming sulfuric acid with the compound having the formula (IV) or(V).

Specifically, the reaction of cationic polymerization and the reactionof sulfonation occur in one and the same reaction solution on thecompound represented by the formula (IV) or (V) to produce the polymerhaving a chemical structure represented by the formula (II) or (III).The produced polymer can be easily converted by neutralization into thepolymer having a chemical structure represented by the formula (I). Thepolymer having structure (II) or (III), therefore, may be utilized inits unmodified form. Since the control of the doping level in thecompound (II) or (III) is easy to effect, it will be more convenient toproduce the polymer having structure (I) by thoroughly effecting theneutralization mentioned above and, whenever necessary, produce thepolymer having structure (II) or (III) from the polymer having structure(I) as mentioned above.

Of the compounds represented by the general formula (IV), thosecompounds having H for both R¹ and R² and S for Y can be easily producedby such known methods as disclosed by J. A. Gladysz et al. inTetrahedron, 35, 2329 (1979), for example.

Of the compounds having the formula (V), those compounds having H forboth R¹ and R² and S for X can be easily produced from the compoundshaving the formula (IV) by such known methods as disclosed by R. Meyeret al. in J. Prakt. Chem., 20, 244 (1963), for example.

The sulfonating agents which are effectively usable herein include, forexample, sulfuric acid, fuming sulfuric acid, sulfur trioxide,chlorosulfonic acid, fluorosulfonic acid, and sulfamic acid. Althoughthe amount of the sulfonating agent to be used herein is notspecifically limited, because it is variable depending the kind ofmonomer and the kind of sulfonating agent, the preferable amount is inthe range between 1.1 to 20 equivalents to the molar amount of themonomer. Optionally, two or more such sulfonating agents may be used incombination.

The concentration of the monomer usable in the production of the polymerhaving a chemical structure represented by the formula (I), (II), and/or(III) is generally desired to be in the range between 10⁻⁴ and 10mol/liter, although it is variable depending upon the kind of monomerand the scale of reaction.

The reaction temperature usable in the production of the polymer havinga chemical structure represented by the formula (I), (II), and/or (III)is not particularly limited but fixed, depending on the particularmethod of reaction to be used. Generally, the reaction temperature ispreferably in the range between -80° C. and 250° C., more preferablybetween -30° C. and 150° C. The polymerization time is preferably in therange between 0.01 hour and 200 hours, although it is variable de endingupon the method of polymerization, the temperature of polymerization orthe monomer and cannot be generally defined.

The solvent usable in the polymerization reaction for the production ofthe polymer having a chemical structure represented by the formula (I),(II), and/or (III) from the compound having the formula (IV) or (V)cannot be generally defined because it is variable, similarly to thepolymerization temperature and the polymerization time, depending uponthe sulfonating agent and the monomer to be used in the polymerizationreaction. The solvent is only required to be capable of dissolving themonomer and the sulfonating agent and to be one inhibiting neither thereaction of sulfonation nor the polymerization reaction. Morespecifically, the solvents which are effectively usable herein include,for example, water, sulfuric acid, fuming sulfuric acid, formic acid,acetic acid, propionic acid, acetic anhydride, ethers such astetrahydrofuran, dioxane and diethyl ether, polar solvents such asdimethyl formamide, acetonitrile and benzonitrile, esters such as ethylacetate and butyl acetate, and non-aromatic chlorine type solvents suchas chloroform and methylene chloride. Optionally, these solvents may beused in the form of any mixture thereof.

Further, in order to prevent the formation of sulfone compound as aby-product which is known to be formed during the reaction ofsulfonation, any known inhibitory compound may be added upon and duringthe sulfonation and polymerization reactions. Although the inhibitorycompound to be used herein and its amount are variable depending uponthe sulfonating agent and monomer, specific examples of such compoundsinclude fatty acids, organic peroxides, fatty acid anhydrides, pyridine,acetic acid, ketones and the like, effectively usable in the rangebetween 0.01 and 5 mole %.

The polymer having a chemical structure of the formula (I), (II), or(III) is soluble in water and may include one which is also soluble inorganic solvents. In the case of the polymer which is prepared in theform of an aqueous solution, it can be separated and purified byultrafiltration, dialysis, and/or ion exchange operation. In the case ofthe polymer which is prepared in the form of precipitate from thesolvent used in the reaction, it can be separated and purified byfiltration, reprecipitation, and/or solvent fractionation.

The polymer according to the present invention may be a copolymer withanother monomer which is capable of imparting to the copolymer amain-chain structure possessing a π-electron conjugate system, or acopolymer which contains, for example, isothianaphthenylene,isobenzofurylene, isobenzoindolylene, isobenzoselenylene,isobenzoterullylene, thienylene, pyrrolylene, furylene, selenylene,terullylene, iminophenylene, phenylene, vinylene and/or ethynylenestructures in the polymer main chain. It should be noted that thecopolymers are not limited to these examples. The copolymer can beproduced by allowing such a heterocyclic monomer as one which generatesthe main-chain structure as mentioned above to coexist in the reactionmixture of polymerization reaction described herein.

When such a heterocyclic monomer as one which produces the main-chainstructure as mentioned above is copolymerized by the method describedabove with the compound having the formula (IV) or (V), the product ofthis copolymerization is a polymer containing one structure having theformula (I), (II), and/or (III) or a polymer containing two or more suchstructures.

The polymers, including copolymers, having the chemical structurerepresented by the formula (I), (II) and/or (III) and obtained by theabove-mentioned production method generally exhibit high degrees ofsolubility in water. When the symbol M in the general formula ishydrogen, some of the polymers produced assume the form of gel in a highconcentration. The solubility in a solvent and the affinity to thesolvent of the polymers may be varied depending upon the symbol M.

From the polymers having the chemical structure represented by theformula (I), (II), or (III) or copolymers thereof, owing to theirsolubility in water, films, linear shaped articles such as fibers, orbulky shaped articles such as rods, plates, sheets and other solidarticles can be easily manufactured by the molding or film makingmethods which are known in the plastic industry.

The concentration of the solution to be used in said molding or filmmaking methods is preferably in the range between 0.5% and 60% byweight, although it is variable depending upon the condition of molding,the chemical structure of polymer, or the kind of solvent. The moldingor film making process is preferably carried out in an atmosphere ofinert gas or under vacuum. A film of the polymer can be produced bypreparing a solution of the polymer in an appropriate solvent andcasting the polymer in an appropriate solvent and casting the polymersolution on a proper medium such as, for example, a glass plate orsodium bromide disc. Fibers or a bulky shaped article of the polymer isproduced by directly shaping the polymer solution in a desired shape.The polymer, when necessary, may be stretched to a desired shape.

Furthermore, according to the present invention, the water-solubleconducting polymer can be processed to similar articles as above whichcomprise such a water-soluble conducting polymer and another polymersuch as polyvinylalcohol in an optional ratio, for example, bydissolving or mixing the former and the latter in an appropriate solventand processing the polymers contained in the resulting solution (or themixture) into a desired shaped article by a similar method as above. Insuch a case, the amount of said another polymer may preferably be usedin the range between 10 and 500% by weight of the water-solubleconducting polymer. The solvent used herein is preferably water, but isnot limited to water and may be selected from any other solvents or maybe a mixed solvent, provided that the polymer has sufficient solubilityin such a selected solvent for processing a shaped article.

The shaped articles manufactured by the above-mentioned processes havequite stable conductivity during the long period of time.

The present invention is based on the principle that the novelwater-soluble electroconductive polymer having a chemical structurerepresented by the formula (I) can be obtained by reacting a sulfonatingagent with the bicyclic heterocyclic monomer compound having the formula(IV) or (V). The polymer is obtained, for the first time, solely by theparticular reaction in which the reaction of sulfonation and thepolymerization reaction are simultaneously effected by directly reactingthe sulfonating agent on the monomer compound.

The polymer having the chemical structure represented by the formula (I)converts itself into the water-soluble electroconductive polymer havingthe chemical structure represented by the formula (II) or (III) bydoping, thereby the conductivity of the polymer is remarkably increased.This novel polymer can be reverted to the original polymer having thechemical structure represented by the formula (I) by either remarkablyincreasing electroconductivity or de-doping.

EXAMPLES

The present invention will now be further illustrated by, but is by nomeans limited to, the following Examples.

Example 1

Process for production of the polymer having a chemical structurerepresented by the formula (I), having H for both R¹ and R², S for X,and Na⁺ for M.

To 2.0 g of fuming sulfuric acid (20% SO₃) kept at 10° C., 550 mg (4.0mmol) of 1,3-dihydroisothianaphthene, a known compound, was slowly addedas stirred. When the resultant mixture was allowed to cool to a roomtemperature and was continued to stir for one hour, the reactionsolution became a reddish purple color. The reaction solution, whenheated to 70° C., was changed to a dark blue color. After 30 minutes, itwas turned into a solid substance. The resultant reaction mixture wasplaced in 100 ml of 0.1N NaOH/methanol to be neutralized andprecipitated therein. The precipitate was separated with a centrifugalseparator. The solid reaction product was dissolved in 100 ml of waterand the resultant aqueous solution was treated with a dialysis membraneto remove sodium sulfate as foreign matter. The dialyzed solution wasallowed to evaporate under a reduced pressure to remove the solventtherefrom and then dried under vacuum, to obtain 430 mg of a black Naform polymer (yield 45%).

The polymer thus produced yielded a UV spectrum illustrated in FIG. 1.The molecular weight distribution of the polymer measured by GPC isillustrated in FIG. 2. The IR spectrum of the polymer is illustrated inFIG. 3. FIG. 4 shows the cyclic voltammogram performed on a polymer film(polymer film/ITO glass operating electrode, platinum counter electrode,silver/silver ion reference electrode in acetonitrile, borofluoricacid-acetonitrile electrolyte, scanning speed 50 mV/sec.). The graphindicates that the polymer, in a cycle between -0.2 V and 0.7 V underfixed conditions, can be electrochemically doped and dedoped.

Elementary analyses (%) for C₈ H₃ S₂ O₃ Na Calculated: C; 41.02%, H;1.298, S; 27.38%, Na; 9.82% Found: C; 40.57%, H; 1.51%, S; 27.55%, Na;9.38%

Example 2

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², S for X, andH⁺ for M.

An aqueous solution was prepared by dissolving 380 mg of a reactionmixture obtained in the same manner as in Example 1 in about 1,000 ml ofwater and adjusting a pH of the solution to 1.9 with hydrochloric acid.The aqueous solution was purified and concentrated by ultrafiltration.The concentrate was allowed to evaporate under a reduced pressure toremove water and dried under vacuum, to obtain 320 mg of a blackpolymer.

The UV spectrum of the polymer produced above is illustrated in FIG. 5.When the polymer was then adjusted to a pH value of about 8 by additionof aqueous NaOH, the UV spectrum of the polymer in the solution waschanged to that which is illustrated in FIG. 1.

Example 3

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², S for X, andH⁺ for M.

An aqueous solution of acid form polymer was obtained by dissolving 200mg of a polymer prepared in the same manner as in Example 1 in 50 ml ofwater and subjecting the resultant solution to an ion-exchange treatmentusing an H form cation-exchange resin (Amberlite IR-120B). When thisaqueous solution was allowed to evaporate under a reduced pressure toremove water and dried under vacuum, 180 mg of a black polymer wasobtained. The spectrum of the produced polymer was similar to that shownin FIG. 5.

Example 4

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², S for X, andH⁺ for M.

In 4.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid(20% SO₃), 500 mg of 1,3-dihydroisothianaphthene was slowly added asstirred at a room temperature and then continuously stirred overnight.The resultant reaction solution exhibited a red color. When it was thenheated to 90° C., it changed a dark blue color at once. After threehours, it was turned into a dark blue homogeneous solution.

Further, the reaction mixture was heated and stirred at the sametemperature for two hours and then poured into 1,000 ml of water. Theresultant aqueous solution was adjusted to pH 1.9, purified with anultrafilter membrane and concentrated to 100 ml. The concentrate wasallowed to evaporate under a reduced pressure to remove water and driedunder vacuum, to obtain 390 mg of a black polymer.

The UV spectrum and the IR spectrum of the polymer produced above weresimilar to those obtained in Example 2.

Elementary analysis (%) for C₈ H₄ O₁.65 S₁.55 Calculated: C; 54.54%, H;2.27%, S; 28.18% Found: C; 55.33%, H; 2.98%, S; 27.45%

Example 5

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², S for X, andNa⁺ for M.

To 2.0 g of fuming sulfuric acid (20% SO₃) kept at 10° C., 500 mg (4.0mmol) of 1,3-dihydroisothianaphthene-2-sulfoxide, a known compound, wasslowly added as stirred. The resultant mixture was allowed to cool toroom temperature and stirred continuously for one hour. The reactionsolution exhibited a reddish purple color. When the reaction solutionwas then heated to 80° C., it changed to a dark blue color. After 30minutes, it was turned into a solid substance. The resultant reactionmixture was placed in 100 ml of 0.1N NaOH/methanol. The precipitate wasdissolved in 100 ml of water, dialyzed to expel excess sodium sulfate,then the dialyzed solution was allowed to evaporate under a reducedpressure to remove the solvent, and dried under a vacuum to obtain 430 mg of a black polymer.

The UV spectrum and the IR spectrum of the produced polymer were similarto those obtained in Example 1.

Elemental analyses (%) for C₈ H₂.88 O₃.36 S₁.12 Na₁.12 Calculated: C;44.81%, H; 1.34%, S; 16.73%, Na; 12.02% Found: C; 44.21%, H; 1.13%, S;16.53%, Na; 12.84%

Example 6

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², S for X, andNa⁺ for M.

To 8 ml of sulfuric acid containing 2.0 g of fuming sulfuric acid (20%SO₃) kept at 0° C. in an atmosphere of nitrogen, 400 mg ofisothianaphthene, a known compound, was slowly added as stirred. Whenthe resultant mixture was stirred continuously for eight hours, theresultant reaction solution exhibited a red color. When the reactionsolution was then allowed to cool to room temperature and subsequentlyheated to 90° C., it exhibited a dark blue color. After five hours, itturned into a homogeneous black solution.

The reaction mixture was poured into 100 ml of 0.1N NaOH/methanol. Theprecipitate was centrifugally separated. The solid centrifugate wasdissolved in 100 ml of water, dialyzed to remove excess sodium sulfate,then the dialyzed solution was allowed to evaporate under a reducedpressure to remove water, and dried under a vacuum to obtain 220 mg of ablack polymer.

The UV spectrum and the IR spectrum of the produced polymer were similarto those obtained in Example 1.

Example 7

Conversion of the polymer having a chemical structure represented by theformula (I) to the polymer having a chemical structure represented bythe formula (II) and/or formula (III).

A polymer film was manufactured by dissolving 50 mg of a polymerprepared in the same manner as in Example 1 in 2 ml of water and castingthe resultant aqueous solution on an ITO glass plate by spin-castingmethod. An electrochemical cell was constructed by using the film-coatedITO glass plate as a working electrode, a platinum wire as a counterelectrode, and a silver/silver ion electrode as a reference electrode.When a potential of 0.5V was applied electrochemically to the cell at aroom temperature in a 0.5 mol/liter HBF₄ /acetonitrile solution (havinga water content of 6%), the film which was in a blue color turned to agrayish black color.

Example 8

Conversion of the polymer having a chemical structure represented by theformula (I) to the polymer having a chemical structure represented bythe formula (II) and/or formula (III).

A polymer film was manufactured by dissolving 50 mg of a polymerprepared in the same manner as in Example 3 in 2 ml of water and castingthe resultant aqueous solution on a platinum foil by spin-castingmethod. An electrochemical cell was constructed by using the film-coatedplatinum foil as a working electrode, a platinum wire as a counterelectrode, and a silver/silver ion electrode as a reference electrode.When this cell was electrically scanned at a room temperature in a 0.1mol/liter tetrabutylammonium perchlorate/acetonitrile solution, toconfirm the occurrence of the same H⁺ -popping as described in "J. Am.Chem. Soc.", 110, 2983 (1988). The detection of the release of H⁺indicates that the film possessed a self-doping function. Thus, theproduction of the polymer having the chemical structure represented bythe formula (II) was accomplished.

Example 9

Conversion of the polymer having a chemical structure represented by theformula (I) to the polymer having a chemical structure represented bythe formula (III).

A polymer film was manufactured by dissolving 100 mg of a polymerprepared in the same manner as in Example 1 in 2 ml of water and castingthe resultant aqueous solution on a glass plate by spin-casting method.When iodine was allowed to affect this film in a gaseous phase, thecolor of the film changed from blue to light blackish gray. Theelectroconductivity (determined by four-probe method) at a roomtemperature rose from σ=5×10⁻⁵ S/cm to σ=8×10⁻¹ S/cm. Thereafter, thefilm was separated from the glass plate and subjected to elementaryanalysis.

Elementary analyses (%) for C₈ H₃ S₂ O₃ NAI₀.3 Calculated: C; 35.25%, H;1.10%, S; 23.49%, Na; 8.42%, I; 13.95% Found: C; 35.47%, H; 1.34%, S;23.55%, Na; 7.98%, I; 13.74%

Example 10

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for both R¹ and R², NR³ for X,CH₃ for R³, and Na⁺ for M.

To 4.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid(20% SO₃), 500 mg of N-methylisoindoline produced by the known methodreported as in Adv. Heterocycl. Chem., 10, 113 (1969) was placed slowlyadded as stirred at a room temperature, and stirred continuously forfive hours at a room temperature. When the resultant reaction mixturewas then heated to 90° C. for three hours, the reaction solutionexhibited a black color.

The reaction mixture was poured into 100 ml of methanol. The precipitateconsequently formed was centrifugally separated. The solid centrifugatewas dissolved in 100 ml of 0.5N aqueous sodium hydroxide solution,dialyzed to remove excess sodium sulfate and sodium hydroxide, then thedialyzed solution was allowed to evaporate under a reduced pressure toremove the solvent, and dried under vacuum, to obtain 380 mg of a blackpolymer.

IR: (KBr disk, cm⁻¹ ); 1803w, 1412w, 1314m, 1225w, 1194s, 1042s, 750s

Example 11

Process for production of the polymer having a chemical structurerepresented by the formula (I) having H for R¹, O(CH₂)₉ CH₃ for R², Sfor X, and Na⁺ for M.

To 8.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid(20% SO₃) kept at 0° C., 500 mg of5-decyloxy-1,3-dihydroisothianaphthene produced by a known method asreported in JP-A-2-242816 was slowly added as stirred and thencontinuously stirred for one hour. When the resultant mixture was thenheated to 90° C. for 30 minutes, the reaction solution turned black.

The resultant reaction mixture was poured into 100 ml of 0.5N aqueousNaOH/methanol solution and the precipitate was separated centrifugally.The solid centrifugate consequently obtained was dissolved in 100 ml ofwater, dialyzed to remove excess sodium sulfate, then the dialyzedsolution was allowed to evaporate under a reduced pressure to remove thesolvent, and dried under vacuum to obtain 150 mg of a black polymer. TheUV spectrum of the produced polymer was similar to that obtained inExample 1.

Example 12

On the surface of a glass plate as a support, 10% by weight of anaqueous solution of a water-soluble conducting polymer prepared in thesame manner as in Example 2 was applied and left drying thereonspontaneously. The applied layer of the polymer was dried under vacuumand separated from the glass plate, to obtain a free-standing film ofabout 20 μm in thickness. The electroconductivity of this film(determined with d four-terminal testing system) at a room temperaturewas a σ=1.4 S/cm. The conductivity of the film remained stable when itwas kept in air for two months.

Example 13

On the surface of a glass plate as a support, an aqueous solution of 1%by weight of a water-soluble conducting polymer produced in the samemanner as in Example 2 was applied by the use of a spin coater at a 35room temperature and a revolution number of 1,000 rpm to form a thinfilm of about 0.05 μm in thickness (determined by the needle touchmethod called Dektak). This thin film exhibited good adhesiveness to theglass plate support and showed surface resistance of about 7.8×10⁵ Ω/□.The transmittance of the film at 500 nm in a visible ray region was 96%.Thus, the polymer yielded a conducting film of extremely hightransparency.

Thin films were prepared in the same manner as above except for therevolution number of a spin coater and the properties of the filmsobtained are 10 shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Revolution                                                                              Film        Surface  Transmittance                                  Numbers   Thickness   Resistance                                                                             (%, at                                         (rpm)     (μm)     (Ω/□)                                                                 500 nm)                                        ______________________________________                                        200       0.25        1.5 × 10.sup.5                                                                   83                                             500       0.10        3.8 × 10.sup.5                                                                   93                                             1000      0.05        7.8 × 10.sup.5                                                                   96                                             ______________________________________                                    

Example 14

On the surface of a glass plate as a support, an aqueous solutioncontaining 1% by weight of a water-soluble conducting polymer producedin the same manner as in Example 2 and 1% by weight of polyvinylalcohol(degree of polymerization of 500) was applied by the use of a spincoater at a room temperature at a revolution number of 1,000 rpm to forma thin film of about 1 μm in thickness, determined in the same manner asin Example 13. This thin film exhibited good adhesiveness to the glassplate support and showed surface resistance of about 1×10⁷ Ω/□. Thetransmittance of the film at 500 nm in a visible ray region was 97%.

Example 15

The water-soluble conducting polymer produced in the same manner as inExample 2 was not only soluble in water but also in dimethylformamide(DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) and methanolrespectively.

Example 16

An aqueous solution containing 5% by weight of a water-solubleconducting polymer produced in the same manner as in Example 10 and 20%by weight of polyvinylalcohol (degree of polymerization of 2000) wasplaced in a Petri dish of a diameter of about 5 cm) and was allowed toevaporate to remove water and then dried under vacuum. A shaped plate(disc) of about 1 mm in thickness as formed in the dish was separatedfrom the bottom of the dish. This shaped article showed surfaceresistance of about 8×10⁸ Ω/□.

Example 17

An aqueous solution containing 10% by weight of a water-solubleconducting polymer produced in the same manner as in Example 1 and 12%by weight of polyvinylalcohol (degree of polymerization of 2000) wasplaced in a syringe having a muzzle diameter of about 1 mm, and thesolution was slowly extruded into ethanol and kept for a day. A fibrousshaped article formed was then removed from the solvent, and dried toobtain blackish blue fiber. The fiber had electroconductivity ofσ=2×10⁻⁶ S/cm, measured by four-probe method, at a room temperature.When iodine was allowed to affect this fiber in a gaseous phase in thesame manner as in Example 9, the electroconductivity at a roomtemperature rose to σ=5×10⁻² S/cm.

This fiber was drawn at a draw ratio of 1.5 at a room temperature, andthe electroconductivity of the resultant fiber rose to 0.3 S/cm.

Example 18

On the surface of a glass plate as a support, an aqueous solution of awater-soluble conducting polymer produced in the same manner as inExample 2 and polyvinylalcohol (degree of polymerization of 500) ascomposed at various ratio was applied by the use of a spin coater at aroom temperature and a revolution number of 1,000 rpm. The surfaceresistance of the thin films obtained is shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Water-soluble                                                                 Conducting Polymer                                                                          Polyvinylalcohol                                                                          Surface Resistance                                  ______________________________________                                        1 wt %        1 wt %      1 × 10.sup.7 Ω/□             1 wt %        5 wt %      3 × 10.sup.7 Ω/□             1 wt %        10 wt %     3 × 10.sup.8 Ω/□             ______________________________________                                    

Example 19

Production of a compound represented by formula (X), which is a compoundrepresented by formula (VI) wherein r in 0 (R⁴ ═R⁵ ═R⁶ ═H, X¹ ═X² ═X³═X⁴ ═H, M¹ ═Na⁺):

To 4 ml of a fuming sulfuric acid (20% SO₃) cooled to 20° C. or lower, 1g of 1,3-dihydroisothianaphthene, which is a known compound, wasgradually added with stirring, followed by stirring for 4 hours at aroom temperature. The reaction mixture was poured into 150 ml of icewater, and thereto was added 20 g of sodium chloride to salt out sodium1,3-dihydroisothianaphthene-5-sulfonate, which was then isolated by acentrifugal separator and vacuum dried to obtain 850 mg of a gray powdercompound.

Example 20

Production of a polymer comprising a chemical structure represented bythe following formula (XII), which is a formula represented by formula(VII) wherein r in 0 (R⁴ ═R⁵ ═R⁶ ═H, M═H⁺): ##STR14##

To a mixed system of 5.5 g of ferric chloride, 1 ml of an aqueoussolution of hydrogen peroxide (30%), and 10 ml of water, 1 g of sodium1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner asin Example 19, was gradually added with stirring. After continuingstirring one day at a room temperature, a viscous black reactionsolution was obtained.

The reaction mixture was vacuum dried, and then poured into 100 ml ofacetone, and the precipitated polymer was separated by a centrifugalseparator. After drying, the polymer was dissolved in 700 ml of a 0.1Naqueous NaOH solution, insoluble materials were removed bycentrifugation, and impurities were removed by passing the solutionthrough a 1-μm filter film. Further, Na⁺ ions were converted into H bymeans of an H-type ion-exchange resin (Amberlite IR-120B). Water wasdistilled off from the aqueous solution, and the residue was vacuumdried to obtain 0.2 g of a blue polymer.

The substitution ratio of the sulfonic acid group of the repeating unitsin the polymer was determined by neutralization titration using alkali,and the polymer was found to consist of almost 100 mol % of therepeating units having substitution by the sulfonic acid group. Thepolymer was subjected to GPC measurement, and found to have anumber-average molecular weight of 18,000 (calculated in terms of sodiumpolystyrenesulfonate as a molecular weight standard material).

Example 21

Production of a polymer comprising a chemical structure represented byformula (IX), which is a formula represented by formula (VIII) wherein ris 0 (R⁴ ═R⁵ ═R⁶ ═H, M¹ ═Na⁺, p=0.8, q=0.2,Ar=1,3-isothianaphthenylene):

To 25 ml of sulfuric acid kept at 10° C. or lower, 1 g of sodium1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner asin Example 19, was gradually added with stirring. After the stirring for1 hour at room temperature, the reaction solution became reddish violet.The solution was then heated at 80° C. for 2 hours, and the resultingblack reaction mixture was poured into 60 ml of 0.1N NaOH/MeOH. Theprecipitated polymer was isolated by a centrifugal separator, dissolvedinto 100 ml of water, and passed through a dialysis membrane to removesodium sulfate as an impurity. After distilling off water from theaqueous solution, the residue was vacuum dried to obtain 0.3 g of a bluepolymer. The visible near infrared absorption spectrum of the resultingpolymer is shown in FIG. 6.

    ______________________________________                                        Elemental analysis for (C.sub.8 H.sub.3 S.sub.2 O.sub.3 Na).sub.0.8           (C.sub.8 H.sub.4 S).sub.0.2 :                                                          C    H           S      Na                                           ______________________________________                                        Calcd.     44.27  2.96        26.59                                                                              8.48                                       Found      44.52  3.23        26.41                                                                              8.92                                       ______________________________________                                    

Thereafter, in order to measure the substitution ratio of the sulfonicacid group of the repeating units in the polymer, 0.2 g of the resultingpolymer was dissolved into water and converted from the Na⁺ form to theH⁺ form by means of an H-type ion-exchange resin (Amberlite IR-120B).After distilling off water from the aqueous solution, the residue wasvacuum dried to obtain 120 mg of a blue polymer.

The substitution ratio of the sulfonic acid group was determined byneutralization titration, and the polymer was found to be a copolymerhaving an average molar fraction of 0.8 of the repeating unit havingsulfonic acid substitution. This reveals that a part of the sulfonicacid split off during the polymerization reaction.

Example 22

Production of a polymer comprising a chemical structure represented byformula (IX), which is a formula represented by formula (VIII) wherein rin 0 (R⁴ ═R⁵ ═R⁶ ═H, M¹ ═H⁺, P=0.6, 9=0.4, Ar=1,3-isothianaphthenylene)

To 5 ml of sulfuric acid kept at 10° C. or lower, 0.7 g of sodium1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner asin Example 19, and 0.28 g of 1,3-dihydroisothianaphthene were graduallyadded with stirring. After the stirring for 1 hour at room temperature,the reaction solution turned violet, and when heated at 90° C. for 3hours thereafter, the reaction solution changed to black. The resultingreaction mixture was poured into 60 ml of 0.1N NaOH/MeOH, and theprecipitated polymer was isolated by a centrifugal separator. Thepolymer was dissolved into 100 ml of water, and passed through adialysis membrane to remove sodium sulfate as an impurity. Then, the Na⁺ion was converted to H⁺ by means of an H-type ion-exchange resin(Amberlite IR-120B). After distilling off water from the aqueoussolution, the residue was vacuum dried to obtain 0.5 g of a bluepolymer. The visible near infrared absorption spectrum of the resultingpolymer is shown in FIG. 7.

The substitution ratio of the sulfonic acid group was determined byneutralization titration, and the polymer was found to be a copolymerhaving an average molar fraction of 0.6 of the repeating unit havingsulfonic acid substitution.

Example 23

Production of a compound represented by formula (XI), which is acompound represented by formula (VI) wherein r is 1 ((R⁴ ═R⁵ ═R⁶ ═H, X¹═X² ═X³ ═X⁴ ═H, M¹ ═Na⁺):

Example 19 was repeated except for using 1 g of 1,3-naphtho2,3-c!thiophene, which is a known compound, in place of1,3-dihydroisothianaphthene, and sulfonation was carried out on theresulting solution in the same manner as in Example 19 to obtain 420 mgof sodium 1,3-naphtho 2,3-c!thiophenesulfonate as a gray powder.

Example 24

Production of a polymer comprising a chemical structure represented bythe following formula (XIII), which is a formula represented by formula(II) wherein r is 1 (R⁴ ═R⁵ ═R⁶ ═R⁷ ═R⁸ ═H, M¹ ═NH₄ ⁺): ##STR15##

Example 20 was repeated except for using 700 mg of sodium1,3-dihydronaphtho 2,3-c!thiophene-6-sulfonate, produced in Example 24,as a monomer in place of 1,3-dihydroisothianaphthene. Polymerization andsubsequent procedures were conducted in the same manner as in Example20, and 200 mg of an acid-form polymer was obtained. The sulfonic acidsubstitution ratio of the repeating units thereof was almost 100%. Thepolymer was dissolved in water, an excess amount of aqueous ammonium wasadded thereto, and the resulting mixture was distilled off under reducedpressure to obtain a polymer of an ammonium salt. The polymer was againdissolved in water and its visible near infrared absorption spectrum wasmeasured. The results are shown in FIG. 8.

Example 25

Production of a compound represented by formula (X), which is a compoundrepresented by formula (I) wherein r in 0 ((R⁴ ═R⁵ ═R⁶ ═H, X¹ ═X² ═X³═X⁴ ═H, M¹ ═(CH₃)₃ (n--C₈ H₁₇)N⁺ :

3 g (12.7 mmol) of sodium 1,3-dihydroisothianaphthene-5-sulfonate wasdissolved into 100 ml of purified water while keeping the temperature at20° C., and thereto was added 3.20 g (12.7 mmol) ofn-octyltrimethylammonium bromide (produced by Tokyo Kasei Co., Ltd.)with stirring. After 30 minutes, the mixture was extracted three timeswith chloroform (20 ml×3 times), and then the chloroform layer was driedover anhydrous sodium sulfate and distilled off under reduced pressureto obtain an ion complex form as an oily semisolid (gain: 4.35 g, yield:89%). The polymer obtained was found to be soluble in-chloroform,toluene, dimethyl sulfoxide, tetrahydrofuran and dimethylformamide.

Example 26

Production of a polymer comprising a chemical structure represented byformula (X II), which is a formula represented by formula (VII) whereinr in 0, from a compound represented by formula (VI) wherein r in 0, X¹and X³ each is Cl, and X² and X⁴ each is H ((R⁴ ═R⁵ ═R⁶ ═H, M¹ ═Na⁺):

To 4.35 g of the ion complex form obtained in Example 25, 20 ml of a drychloroform was added and 3.17 g (23.7 mmol) of N-chlorosuccinimide (NCS)was further added. At this time, ammonium1,3-dichloroisothianaphthene-5-sulfonate was produced in the system butnot isolated, and after heating the system under reflux for 2 hours, ablack blue solution was obtained. After cooling, insoluble materialswere removed from the reaction solution, the organic layer was driedunder reduced pressure, and 200 ml of 0.1N NaOH was added to thesolution to obtain a water-soluble polymer solution. The resultingsolution was passed through an acidic ion-exchange column, and anacid-form aqueous polymer solution having a pH of 1.8 was obtained. Thevisible near infrared absorption spectrum of the resulting solution gavethe same doped curve as in FIG. 7.

Example 27

An aqueous solution of a 10 wt % electroconductive polymer produced inthe same manner as in Example 4 was coated on the surface of a glassplate as a substrate and dried. After further vacuum drying, the polymerlayer was peeled off from the glass plate to obtain a self-standing filmhaving a thickness of about 30 μm. The self-standing film had anelectric conductivity (in a four-terminal measurement system) at roomtemperature of σ=5×10⁻² S/cm. The electric conductivity value of theself-standing film was constantly maintained in air at room temperaturefor 3 months.

Example 28

Production of a compound represented by formula (X), which is a compoundrepresented by formula (VI) wherein r in 0 ((R⁴ ═R⁵ ═R⁶ ═H, X¹ ═X² ═X³═X⁴ ═H, M¹ ═Na⁺):

To 8 ml of a sulfuric acid solution containing 2 ml of fuming sulfuricacid (20% SO₃) cooled to 20° C. or lower, 500 mg of5-decyloxy-1,3-dihydroisothianaphthene, which is a known compound, wasgradually added with stirring, followed by stirring for 3 hours at roomtemperature. The reaction mixture was poured into 100 ml of ice water,and thereto was added 14 g of sodium chloride to salt out sodium5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonate, which was thenisolated by a centrifugal separator and vacuum dried to obtain 180 mg ofa gray powder compound.

Example 29

Production of a polymer containing a chemical structure represented bythe following formula (XII), which is a formula represented by formula(VII) wherein r in 0 ((R⁴ ═C₁₀ H₂₁)--, R⁵ ═R⁶ ═H, M¹ ═Na⁺): ##STR16##

To a mixture system of 600 mg of ferric chloride, 1 ml of water, 100 mgof sodium 5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonate, wasgradually added with stirring. After continuing stirring 30 min. at roomtemperature, a viscous black reaction mixture was obtained.

The reaction mixture was poured into 10 ml of acetone, and theprecipitated polymer was separated by a centrifugal separator. Afterdrying, the polymer was dissolved in 100 ml of a 0.1N aqueous NaOHsolution, insoluble materials were removed by centrifugation, andimpurities were removed by passing the solution through a 1-μm filterfilm. An alkaline solution containing the polymer was acidified with a1N HCl solution to convert it into an H-type polymer. The aqueoussolution was extracted with chloroform 3 times to provide 55 mg of thepolymer after evaporation.

Example 30

On the surface of a glass plate as a support, an aqueous solution of 1%by weight of the water-soluble conducting polymer produced in the samemanner as in Example 2 was applied by the use of a spin coater at roomtemperature and a revolution number of 1,000 rpm to form a thin film ofabout 0.05 μm in thickness (determined by the needle touch method calledDektak).

This thin film exhibited good adhesiveness to the glass plate support,and showed a surface resistance of about 7.6×10⁵ Ω/□. The transmittanceof the film at 500 nm in the visible region was 96%. Thus, the polymeryielded an conducting film of extremely high transparency.

Thin films were prepared in the same manner as above except for therevolution number of the spin coater. The properties of the filmsobtained are shown in Table 3 below.

                  TABLE 3                                                         ______________________________________                                        Revolution                                                                              Film        Surface                                                 Numbers   Thickness   Resistance                                                                             Transmittance                                  (rpm)     (μm)     (Ω/□)                                                                 (%, at 500 mn)                                 ______________________________________                                         500      0.10        4.2 × 10.sup.5                                                                   93                                             1000      0.05        7.6 × 10.sup.5                                                                   96                                             ______________________________________                                    

The electroconductive polymer produced according to the process of thepresent invention is a water-soluble and/or organic solvent-solubleelectroconductive polymer having excellent processability. Accordingly,the polymer is useful in various electroconductive materials or opticalmaterials which require a precise processing, such as an electrode, asensor, an electronics display element, a non-linear optical element, aphotoelectric conversion element, or an antistatic agent. Further,according to the process of the present invention, not only ahomopolymer, but also a copolymer can be produced; where thecompositions of the components constituting the π-conjugated main chainskeleton of the copolymer can be easily controlled. Furthermore, thepolymer can have a self-doping function and a stable electricconductivity due to the sulfonic acid group contained in the polymer.Still further, the heteropolycyclic compound having a sulfonic acidsubstituent used as a starting material is very stable, and particularlyuseful for the efficient production of a polymer having a highelectroconductivity under mild conditions.

The electroconductive polymer having a chemical structure represented bythe formula (I), (II) or (III) of the present invention is water-solubleand is a polymer exhibiting high workability and possessing highelectroconductivity. Thus, it is useful as electrodes, electronicdisplay elements, nonlinear optical elements, optical conversionelements, antistatic materials, various conducting materials, andoptical materials which are required to allow precision fabrication.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. An electroconductive polymer comprising at leastone structural unit represented by formula (VII), (VIII) or (IX) as arepeating unit: ##STR17## wherein R⁴, R⁵, R⁶, R⁷ and R⁸ eachindependently represents a monovalent member selected from the groupconsisting of a hydrogen atom, a linear or branched, saturated orunsaturated alkyl, alkoxy or alkyl ester group each having from 1 to 20carbon atoms, SO₃ ⁻ M¹, a halogen atom, a nitro group, a cyano group, aprimary, secondary or tertiary amino group, a trihalomethyl group, and asubstituted or unsubstituted phenyl group wherein said substitutedphenyl group is an alkyl-substituted phenyl group, with the proviso thattwo or more of R⁴, R⁵, R⁶, R⁷ and R⁸ are not SO₃ ⁻ M¹ simultaneously,wherein two of R⁴, R⁵, R⁶, R⁷ and R⁸ may combine with each other at anyoptional position to form at least one divalent chain which forms,together with two carbon atoms of the ring substituted with R⁴ -R⁸ atleast one 3- to 7-membered saturated or unsaturated hydrocarbon ringstructure, and the alkyl group, the alkoxy group, or the alkyl estergroup represented by R⁴, R⁵, R⁶, R⁷ and R⁸ may optionally include acarbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl or iminomoiety; M¹ represents H⁺, an alkali metal ion, or a cation of a Vb Groupelement unsubstituted or substituted with an alkyl group having from 1to 30 carbon atoms, or with an aryl group having from 6 to 30 carbonatoms; Ar represents a repeating unit of a π-electron conjugated systemhaving no sulfonic acid group; r represents an integer of from 0 to 3,and indicates the number of condensed rings enclosed by the thiophenering and the benzene ring having substituents R⁴, R⁵ and R⁶, wherein thecondensed ring in the formula may optionally contain a nitrogen atom oran N-oxide group; and p and q represent molar fractions of therespective repeating units in the copolymer and thus do not denote ablock copolymer.
 2. An electroconductive polymer comprising repeatingstructural units represented by the formula (I): ##STR18## wherein R¹and R² independently represent a hydrogen atom, a linear or branchedalkyl or alkoxy group having 1 to 20 carbon atoms, a primary, secondaryor tertiary amino group, a trihalomethyl group, a phenyl group or asubstituted phenyl groupwherein said substituted phenyl group is analkyl-substituted phenyl group, X represents S, O, Se, Te or NR³, R³represents a hydrogen atom, a linear or branched alkyl group having 1 to6 carbon atoms or a substituted or unsubstituted aryl group wherein saidsubstituted aryl group is an alkyl-substituted aryl group, providingthat the chain in the alkyl group of R¹, R² or R³ or in the alkoxy groupof R¹ or R² optionally contains a carbonyl, ether or amide moiety, Mrepresents H⁺, an alkali metal ion or a cation and m represents anumerical value in the range between 0.2 to
 2. 3. A shaped articlecomprising the electroconductive polymer of claim
 1. 4. A shaped articlecomprising the electroconductive polymer of claim 2.